Method of protecting material against fungi comprising applying a 1, 2-naphthoquinone 2-oxime



METHOD OF PROTECTING MATERIAL AGAINST FUNGI COMPRISING APPLYING A 1,2-NAPH- THOQUINONE 2-OXI1VIE Glentworth Lamb, Stamford, and James W. Clapp,

Darien, Conn., assignors to American Cyanamid Company, New York, NY, a corporation of Maine No Drawing. Application August 20, 1958 Serial No. 756,085

1 Claims. 01. 167-32 This invention relates to fungicides. More particularly, it relates to an improved method and composition for 'thej'prevention and control of fungus infestations of agrifruits and the like can be prevented and controlled to an unusually surprising degree by'the use of a composition containing as an active fungicidal ingredient at least one compound of the formula in which X -X are selected from hydrogen, hydroxy, al-

' koxy and halogen; and the alkalimetal salts thereof.

Typical examples of the fungicides according to the invention are 1,2-naphthoquinone 2-oxime, 4-bromo-l,2- naphthoquinone 2-oxime, S-bromo-1,2-naphthoquinone 2- oxime, -6-bromo-1,Z-naphthoquinone 2-oxime, 3-chlorol,2-naphthoquinone 2-oxime, 4-chloro-1,2-naphthoquinone 2-oxime, -6-chloro-1,2-naphthoquinone 2-oxirne, 8- chloro-1,2-naphthoquinone 2-oxime, S-hydroxy-1,2-naphthoquinone 2-oxime, 6-hydroxy-1,2-naphthoquinone 2- oxime, S-hydroxy-l,2-naphthoquinone 2-oxime, S-methoxy-l,2-naphthoquinone 2-oxime, 7-methoxy-l,2-naphthoquinone 2-oxime, 4-bromo-5-hydroxy-1,2-naphthoquinone 2-oxime, 6,8-dibromo-2-methoxy-1,2-naphthoquinone 2- oxime, and the like; and their alkali metal salts.

In general, the 1,2-naphthoquinone 2-oximes of this invention can be readily synthesized by reacting l-naphthol or a substituted l-naphthol with nitrous acid. The monovalent metal salts can be prepared by mixing an aqueous solution of the metal hydroxide with a concentrated alcoholic solution of the oxime, concentrating if necessary, and recovering the solid product.

It is an advantage of the present invention that the fungicidal compounds are effective in extremely dilute concentrations. Accordingly, they may be employed as compositions comprising any of a variety of suitable carriers or diluents. Such compositions can be prepared either as a suspension or solution in a suitable liquid, or as a dust. A suspension or dispersion of the free oxime in a non-solvent such as water or an aqueous solution of an alkali metal salt thereof can be advantageously prepared for plant foliage treatment.

For the protection offruits, seeds, plant tubers and the like during storage, it is advantageous to treat them by employing an aqueous emulsion of the free oxime or an aqueous solution of the salt. An emulsion may be formed by dissolving the fungicide in an oil and emulsifying the solution in water. The oil which can be used as a solvent for the oximes of the present invention is a' hydrocarbon, as, for example, benzene or toluene or a United States Patent halogenated hydrocarbon, such as chlorobenzene,-chloroform, fiuorotrichloromethane or dichlorodifluoromethane.

Fungicidal dust may also be prepared by mixing the instant oximes or their salts with dusting materials as for example, clay, pyrophyllite, bentonite, pumice, fullers earth and the like. Accordingly, seed can be protected from soil organisms harmful to them by incorporating the persent compounds with a solid carrier and mixing the composition with the seed as by tumbling.

The dosage employed in any particular case will necessarily vary. It is dependent upon the particular oxime compound employed, the material being treated and the method of application. In addition, in the case of ap-- plication to living vegetation'and seeds, the dosage is, also dependent upon the susceptibility of the particular vegetation to the particular oxirne compound, the state and condition of growth of the vegetation as well as: climatic conditions prevailing. The optimimi dosage em-' ployed in each case can readily be determined by those. in general,. when applied as a foliar spray to vegetation, a dosage rate: of from 1-4 lbs. of fungicide per acre is adequate. When. applied to seed, a dosage of about 0.5-4 oz./l00 pounds: of seed is generally employed. The usual practice is to employ about 0.0 005-002 pound of oxime compound perskilled in the art by conventional means.

pound of organic matter being treated.

The concentration of oxime to inert carrier or diluen may likewise be varied. In general, up to about 10% by weight of the oxime compound based upon the weight of the inert carrier is generally quite adequate. In most.

cases, however, from about 0.01% to 1% of active ingredient and preferably about 0.15% is adequate foraqueous dispersionsand solutions. For dust compositions, about 5% of active ingredient is quite satisfactory for most applications.

' When the free oximes are employed as suspensions or emulsions, the compositions may advantageously contain a surface active dispersing agent. Examples of such dis-- persing'or surface active agents well known in the art.

include the fattyacid esters of polyhydric alcohols, the

sodium salt of a polymerized propyl naphthalene sulfonic: acid formed by condensing formaldehyde with propyli naphthalene sodium sulfonate, the alkylarylpolyether al-- Usually, a good practice is to addl from one to about five parts of surface active agent per cohols, and the like.

l00'parts of fungicide compound.

In addition to an oxime compound, a composition ac-- cording to this invention may also contain other active ingredients which, in addition, may serve as the carrier.. These active ingredients in admixture can be herbicides,., Thus, for example. an effective dose of a fungicide according to the present:

insecticides, fertilizers and the like.

an advantage of the present invention that the composi-- tions thereof have both properties to an unusual degree.

This invention is further illustrated by the following; example.

EXAMPLE 1 Tests are conducted to determine the fungicidal activity" of the compounds listed in the following Table I on spores;

of Sclerotinia fructigena and Stemphylium sarcinaeforma. Which are both fungi and parasitic on stone fruits and. clover, respectively. These organisms are cultured on. potato dextrose agar slants. Spores are obtained in abundance from 14 day old cultures of Stemphylium sarcinae- Table 1 Min. Cone. (percent) for 95-100% K111 Compound Sclerotinia fr-uctigena Stemphylium sarcinaeforme B-Hydroxy-l,Z-Naphthoquinone z-oxime. S-Methow-l Z-Naphthoqulnone 2-oxime. 4-Ch1oro-1,2- aphthoquinone 2-oxime.-- sodlium salt; of 1,2-Naphthoquinone 2- ox me EXAMPLE 2 Two week old cucumber plants of the Green Prolific variety are sprayed to run-off with acetone-water solutions containing the compounds of Table II in varying concentrations. After the spray deposits dry, the plants are inoculated with a conidial suspension of cucumber anthracnose fungus (Colletotrichum lagenar'ium). Results appear in Table II.

Table II Percent Disease Number of lesions Cone.

Compound Oontro1(50% Acetone in H20) 4-Oh1oro-L2-naphthoqmnone 2-oxlme--.

G-Hydroxy-LZ-naphthoquinonc 2-oxime.

lS-Methoxy- ,Z-naphthoquinone 2-oxime.

H OIOKO: qmwmawmoao We: claim:

1. A method for protecting organic materials susceptible to attack by fungi which comprises applying to said material at least one member selected from the group consisting of 1,2-naphtho'quinone 2-oximes and the alkali metal salts thereof, said oximes being represented by the formula in which X -X are selected from the group consisting of hydrogen, hydroxy, alkoxy and halogen.

2. A method according to claim 1 in which the mem her is 1,2-naphthoquinone 2-oxime.

3. A method according to claim 1 in which the member is a 4-ha1o-1,2-naphthoquinone 2-oxime. v

4. A method according to claim 1 in which the member is 6-hydroxy-1,Z-naphthoquinone 2-oxime.

5. A method according to claim 1 in which the member is 5-alkoxy-1,2-naphthoquinone 2-oxime.

6. A method according to claim 1 in which the member is a 4-halo-5-hydroxy-1,2-naphthoquinone 2-oxime.

7. A method according to claim 1 in which the member is an alkali metal salt thereof.

References Cited in the file of this patent Elseviers Encycl. of Organic Chem., Series III, vol. 12B, pp. 2730 and 2748, 1952.

Chem. Abst., vol. 15, pp. 2414-16, 1921.

Chem. Abst., vol. 41, p. 1728 1947. 

1. A METHOD FOR PROTECTING ORGANIC MATERIALS SUSCEPTIBLE TO ATTACK BY FUNGI WHICH COMPRISES APPLYING TO SAID MATERIAL AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF 1,2-NAPHTHPQUINONE 2-OXIAMES AND THE ALKALI METAL SALTS THEREOF, SAID OXIMES BEING REPRESENTED BY THE FORMULA 